CN106835326A - High performance Graphene composite polyvinyl alcohol fiber and preparation method thereof, application - Google Patents
High performance Graphene composite polyvinyl alcohol fiber and preparation method thereof, application Download PDFInfo
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- CN106835326A CN106835326A CN201610835198.4A CN201610835198A CN106835326A CN 106835326 A CN106835326 A CN 106835326A CN 201610835198 A CN201610835198 A CN 201610835198A CN 106835326 A CN106835326 A CN 106835326A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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Abstract
The invention provides a kind of preparation method of high performance Graphene composite polyvinyl alcohol fiber, comprise the following steps：The graphite alkenes material aqueous solution is pre-processed, the graphite alkenes material classification aqueous solution is obtained, the D90 norm controllings of graphite alkenes material are below 70 μm；The PVA aqueous solution, boric acid and the graphite alkenes material classification aqueous solution are mixed, the spinning solution of the boronic acid containing that PVA concentration is 10 20wt% is obtained；After by spinning solution filtering, deaeration, spinning and drying, obtain final product.The high performance Graphene composite polyvinyl alcohol fiber prepared using above-mentioned preparation method is widely used in building trade, carrier aspect.The indexs such as composite fibre tensile strength, stretch modulus, the elongation at break have the raising of matter, and also additionally impart fibrous material toughness higher, hot water resistance and antistatic behaviour.
Description
Technical field
It is multiple in particular to a kind of high performance Graphene the present invention relates to vinal processing preparation field
Close vinal and preparation method thereof, application.
Background technology
Polyvinyl alcohol (PVA) is a kind of high molecular weight water soluble polymer, and its molecular formula is [C2H4O]n.Vinal
Due to having good hydrophily, impact resistance and the features such as being easily dispersed property is good in processing and forming, can as plastics, cement with
And the reinforcing material of ceramics etc., also alternative asbestos for having a carcinogen.
Graphene is a kind of two-dimensional material of the alveolate texture being made up of individual layer sp2 hydbridized carbon atoms, with many excellent
Different performance.It has been found since 2004, Graphene just becomes a big study hotspot of scientific circles.In the thing to Graphene
While Physicochemical property is studied, the composite related to Graphene also emerges in an endless stream.On nano science direction, stone
Black alkene is also used to prepare the nano composite material of correlation, especially the nanometer of Graphene/metal or graphene/metal oxide
Composite.Due to the excellent properties of Graphene, these nano composite materials are in novel energy, bio-sensing, catalysis, optics material
There are wide Research Prospects in the fields such as material.
Patent CN104328533 A disclose a kind of system of high-strength and high-modulus weight northylen alcohol-graphene nano composite fibre
Preparation Method, after Graphene or derivatives thereof and polyvinyl alcohol are well mixed in mixed solvent, by the method for gel spinning
Spinning, high power hot-stretch obtains the polyvinyl alcohol-graphene nano composite fibre of high-strength and high-modulus, obtained polyvinyl alcohol-graphite
The tensile strength of alkene nano-composite fiber is up to 1.4-2.2GPa, Young's modulus 36GPa, elongation at break 10%.But the patent
Its intensity of the modified PVA of preparation and toughness are general, await further raising, and its do not possess yet antistatic property etc. other
Excellent properties, it is impossible to meet modern's multi-functional requirement to material in itself.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide the above-mentioned preparation with high performance Graphene composite polyvinyl alcohol fiber
Method, step linking is tight before and after preparation method, and method simple and fast can be realized seamless with existing production process equipment and flow
Docking, has the advantages that the effective ingredient that can completely retain raw material, and, operating condition temperature simply easily operated with method
With industrialized production, the economic benefit for being capable of achieving Graphene composite polyvinyl alcohol fiber are good, the fibrous composite prepared
On the basis of traditional high-strength, high modulus polyvinyl alcohol fibre spinning technique is realized, the mechanical property of further double lifting fiber, together
When impart fibrous material toughness higher, hot water resistance and antistatic behaviour.
The second object of the present invention is to provide one kind to be combined poly- second using high performance Graphene obtained in the above method
The indexs such as enol fiber, the composite fibre slight, elongation at break of stretching have the raising of matter, and also additionally impart
Fibrous material toughness higher, hot water resistance and antistatic behaviour, further expand the market range of application of fibrous material, improve
Value-added content of product, is conducive to further genralrlization application.
The third object of the present invention is to provide the above-mentioned application with high performance Graphene composite polyvinyl alcohol fiber,
The complex fiber material application widely, is widely used in industry-by-industry.
In order to realize above-mentioned purpose of the invention, spy uses following technical scheme：
A kind of preparation method of high performance Graphene composite polyvinyl alcohol fiber is the embodiment of the invention provides, main bag
Include following steps：
(A) the graphite alkenes material aqueous solution is pre-processed, is obtained the graphite alkenes material classification aqueous solution, graphite alkenes
The D90 norm controllings of material are below 70 μm；
(B) the PVA aqueous solution, boric acid and the graphite alkenes material classification aqueous solution are mixed, obtaining PVA concentration is
The spinning solution of the boronic acid containing of 10-20wt%；
(C) after by spinning solution filtering, deaeration, spinning and drying, obtain final product.
High strength poly vinyl alcohol (PVA) fiber has good hydrophily, caking property, impact resistance and processed in itself
It is easily dispersed in journey, institute is as reinforcing material in the side such as cement, Ashestos plate, ceramic building material and polymer matrix composite
Much apply in face.Can effectively improve the shock resistance of material with high intensity PVA fibre reinforced concretes and construction material, resist
The performance such as elastic fatigue and anti-cracking.The geotextiles tensile strength being made of high intensity PVA fibers is high, and creep resistance is good, wear-resisting,
Resistant to chemical etching, resistance to microorganism and transmissibility are excellent, reinforcement, isolation, protection, draining and leakproof can be played in engineering construction and is made
With, can be used for the engineering such as various dams and highway, railway, bridge, tunnel, slurry, sand ground pressure sand water proof, reinforcing, place mat,
Solid base and anti-water segregation etc., can significantly improve construction quality, reduce engineering cost.With epoxy resin by high intensity PVA
Fiber is bonded into shaft instead of the reinforcing bar in concrete, as civil construction project material, can substantially reduce building element
Deadweight.Fracture strength, impact strength, against weather, resistance to corrosion seawater due to high intensity PVA fibers etc. are all relatively good,
Various types of fishing nets, fishing gear, fishing line, cable etc. are suitable for use as, are had at the aspect such as marine fishing and means of transport and well should
Use market.Although the tensile strength and modulus of high intensity PVA fibers are still not as Kevlar, UHMW-PE fiber etc., its fracture ratio
Work(is big, cementability is good, cheap etc., and part fictitious hosts Kevlar fibers higher are possible in terms of composite is protected
Deng.Although high strength poly vinyl alcohol fiber Performance comparision in itself is superior, with the continuous progress of society, to material property
Requirement more and more higher, existing vinal can not meet requirement, develop a kind of new composite extremely urgent.
It is multiple the invention provides a kind of high performance Graphene in order to solve many technical problems present in prior art
The preparation method of vinal is closed, it is fine that the composite fibre that this preparation method is prepared not only possesses traditional polyvinyl alcohol
Tie up all excellent properties of material, and performance also imparts fibrous material toughness higher in itself, resistance to while lifted
The additional properties such as heated aqueous and antistatic behaviour, when preparing Graphene composite polyvinyl alcohol fiber in the prior art, usually directly
Graphene and polyvinyl alcohol are well mixed in mixed solvent, spinning, stretching are obtained the compound fibre of polyvinyl alcohol-graphene nano
Dimension, but the performance of fibrous material that this method is prepared is general, and the present invention is by graphite alkenes material (graphite alkenes material
One or more mixing including Graphene, biomass Graphene, graphene oxide, Graphene derivative, wherein Graphene spreads out
Graphene of the biology including element doping, is finally using graphene-structured therein) with polyvinyl alcohol before, Te Yixian
The aqueous solution of graphite alkenes material is pre-processed, the method for this pretreatment is in the prior art without any record, this hair
It is bright still to belong to pioneering.By after pretreatment to ensure the D90 norm controllings of graphite alkenes material below 50 μm, preferably 30 μm with
Under, in order to the big chip architecture of graphite alkenes material is kept as far as possible, it is ensured that graphite alkenes material will not occur interlayer reunion,
The problem of the stress concentration point fracture that different footpath graphite alkenes materials bring is prevented, if granularity is too big or too small possibility
Will be unfavorable for subsequently forming more homogeneous inorganic-organic bridging arrangement with PVA strands, therefore in order to ensure the equal of piece footpath
One property, more excellent D90 (representing the particle diameter accounted in particle diameter distribution corresponding to 90%) norm controlling between 5-25 μm, can also be
7 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 40 μm, 48 μm etc., more it is held in the graphite alkenes material of same particle diameter just more
After being conducive to subsequently being combined with PVA, the product various aspects of performance for obtaining is all good, it is therefore desirable to strictly control its particle diameter.
The graphite alkenes material that is used includes Graphene, biomass Graphene, graphene oxide, Graphene derivative
One or more mixing, the Graphene derivative is the Graphene by being modified.
Preferably, the Graphene derives any a kind included in element doping Graphene or functional group's graphite alkene thing
Or at least 2 kinds of combination.
Preferably, the element doping Graphene is including in metal-doped Graphene or nonmetal doping Graphene
Any a kind or at least 2 kinds of combination.
The metal-doped metallic element it is typical but non-limiting including potassium, sodium, gold, silver, iron, copper, nickel, chromium titanium,
Vanadium or cobalt.
The nonmetal doping Graphene is typical but non-limiting including nitrogen, phosphorus, boron or silicon.
Preferably, the nonmetal doping Graphene includes nitrogen-doped graphene, phosphorus doping Graphene or sulfur doping
Any a kind or at least 2 kinds of combination in Graphene.
Preferably, functional group's graphite alkene includes being grafted with the Graphene of functional group.
Preferably, functional group's graphite alkene includes any a kind or at least 2 be grafted with hydroxyl, carboxyl or amino
The Graphene of the combination planted.
Hydroxyl of the present invention includes that-R1-OH, the R1 include alkyl, and typical but non-limiting hydroxyl can be
Methylhydroxy, ethyl hydroxy, propyl hydroxy, butylhydroxy, amyl group hydroxyl, hexyl hydroxyl etc..
Carboxyl of the present invention includes that-R2-COOH, the R2 include alkyl, and typical but non-limiting hydroxyl can be with
It is methylhydroxy, ethyl hydroxy, propyl hydroxy, butylhydroxy, amyl group hydroxyl, hexyl hydroxyl etc..
Carboxyl of the present invention includes-R3-NH3, the R3 includes alkyl, and typical but non-limiting hydroxyl can be
Methylhydroxy, ethyl hydroxy, propyl hydroxy, butylhydroxy, amyl group hydroxyl, hexyl hydroxyl etc..
Certainly, during practical operation, the specific preprocess method for using includes：By graphite alkenes material aqueous solution ultrasound point
Retain bottom precipitation after centrifugally operated under the conditions of scattered, 2000-3000rpm, supernatant is centrifuged behaviour under the conditions of 5000-7000rpm
Secondary bottom precipitation and secondary supernatant are respectively obtained after work, wherein the Graphene class material is classified the aqueous solution being sunk including bottom
Any one in shallow lake, secondary bottom precipitation, secondary supernatant is prepared, the aqueous solution prepared by preferably secondary bottom precipitation.
The centrifugally operated speed ratio that the first step obtains bottom precipitation is relatively low, behind the further centrifugally operated of supernatant speed
It is then higher, because the material grainses degree in precipitation is general than larger, if the too fast electrodeposition substance for being unfavorable for bulky grain of speed,
Material grainses degree in follow-up supernatant is typically smaller, therefore speed needs soon, so that the small material of granularity floats
In there is supernatant.So granularity than more consistent graphite alkenes material by after classification in bottom precipitation or at secondary bottom
Portion is precipitated or in secondary supernatant, and the graphite alkenes material classification aqueous solution can select above-mentioned by any of classification treatment
A kind of material, can guarantee that with granularity than more consistent graphite alkenes material, and granularity size also than convenient, with
The homogeneity in piece footpath is fully ensured that, has been conducive to subsequently ensureing the performance of product prepared.
Wherein, the time of ultrasonic disperse be preferably controlled in 1-3h, the time of centrifugally operated is most under the conditions of 2000-3000rpm
Control between 20-40min well, the time of centrifugally operated is preferably controlled between 10-30min under the conditions of 5000-7000rpm,
Control is more conducive to the more thorough of grain size grading treatment within the preferably operating time, so that particle diameter distribution is more uniform.
In addition, the mass percent concentration of the pretreated graphite alkenes material aqueous solution is preferably controlled suitably, because such as
Fruit concentration is too high, and the reunion of piece interlayer, graphene sol liquid (the graphite alkenes material water of low concentration are susceptible in concentration process
Solution) be conducive to the PVA strands to carry out ordering orientation with Graphene as platform is sprawled, it is Graphene addition raw material with the colloidal sol
It is combined with PVA, preferably concentration is below 3wt%, more preferably below 2wt%, further preferably 0.05wt-1.5wt%
Between.
After the graphite alkenes material aqueous solution is pre-processed, first using the PVA aqueous solution and graphite alkenes material of low concentration
The aqueous solution is pre-mixed, and concentration is then stepped up again, finally obtains the spinning solution of the boronic acid containing that PVA concentration is 10-20wt%,
Preferred PVA concentration control disperses complete purpose between 15-16wt% to be reached by way of setting concentration gradient,
If the graphite alkenes material aqueous solution is directly mixed with the PVA aqueous solution of boronic acid containing, such hybrid mode is held very much
Easily there is reunion to be unfavorable for mixing, so as to influence the performance of product, the compound mode of setting gradient concentration of the invention more added with
Be segmented into some gradients beneficial to the performance of final products, during concrete operations, such as successively the PVA aqueous solution of addition 2-5wt%,
The PVA aqueous solution of the PVA aqueous solution, 10-12wt%, 25-40wt% of 6-8wt% etc., the number of gradient is not specifically limited, and rises
Beginning concentration is controlled between 2-5wt%, if after for the easy to operate PVA aqueous solution that can also directly add 2-5wt%, with
The PVA aqueous solution (the concentration maximum pole that the PVA aqueous solution of the boronic acid containing for finally adding is set for gradient of boronic acid containing is directly added afterwards
Limit), if adding the PVA aqueous solution several times, then mix with the graphite alkenes material classification aqueous solution in the PVA aqueous solution
Afterwards, boric acid is finally added again, and the concentration of boric acid is preferably controlled between 2-5wt%.During practical operation, can be according to the reality of technique
Border needs specifically to be adjusted, such as the concentration of PVA sets addition number of times of gradient and PVA solution etc., in a word by using this
The compound mode of this gradient concentration of invention, solves the incomplete problem of Dispersion of Solute Matter in spinning solution, and significantly carry
The performance of Graphene composite polyvinyl alcohol fiber high.
Preferably, in 1-2h, temperature control exists the time control stirred after being added every time when adding the PVA aqueous solution several times
Between 90-100 DEG C, if the too low PVA aqueous solution of temperature cannot be with graphite alkenes material aqueous solution mixing and stirring, it may appear that
The particle of reunion, influences properties of product, therefore temperature to be preferably controlled in suitable scope.
Further, the degree of polymerization of the PVA aqueous solution is preferably controlled between 1700-2500, and alcoholysis degree is preferably controlled in 88-99%
Between, because the degree of polymerization and alcoholysis degree of PVA can significantly affect the tensile strength and stretch modulus of vinal, typically
The degree of polymerization and alcoholysis degree of PVA are higher, and the tensile strength and stretch modulus of vinal are higher.
Filtered in follow-up spinning solution, deaeration, before spinning and drying, preferably first added in spinning solution and handed over
After connection agent acetalization, reducing agent reduction treatment, the purpose for adding crosslinking agent be in order to PVA and Graphene crosslinking so that
Realize macromolecule in the orderly arrangement in nano-graphene piece surface, it is to avoid high molecular entanglement, the height for being conducive to spinning to post-process
Times hot-stretch, so as to improve the performance of PVA fibers., in itself as a kind of inorganic filler, addition reducing agent can for graphite alkenes material
Crosslinking agent is added to belong to preceding crosslinking to improve the hot water resistance of PVA fibers, in spinning solution, also can be after as-spun fibre be prepared
It is crosslinked again, this crosslinking belongs to post-crosslinking, either preceding crosslinking or post-crosslinking can obtain high-performance PVA fibers,
If what is added in spinning solution is graphene oxide, reduction step can be carried out in spinning solution, it is also possible to prepared
Reduced again after fiber, either preceding crosslinking or post-crosslinking, pre reduction still rear reduction is protected in patent of the invention
In the range of shield, crosslinking agent may include one or more mixtures in glyoxal, glutaraldehyde, formaldehyde, boric acid and borax, spinning
The concentration of crosslinking agent is controlled between 0.0075-0.45wt% in stoste, and reducing agent may include sodium borohydride, ascorbic acid, water
One or more mixtures in hydrazine and hydroiodic acid are closed, the concentration of reducing agent is controlled between 0.1-3wt% in spinning solution.
Finally, spinning solution filtered under conditions of 85-120 DEG C, deaeration, be to prevent from freezing the reason for 85-120 DEG C
Glue, in order to avoid being impacted to the performance of fiber, spinning solution is extrusion in the spinneret of 0.08-0.30mm by orifice diameter,
Spun silk becomes as-spun fibre into 40-45 DEG C of saltcake coagulating bath shaping, after as-spun fibre is through pickling, washing, drying, then
Processed by hot-stretch and thermal finalization, that is, obtain high performance Graphene composite polyvinyl alcohol fiber.By control PVA amount and
The amount of graphite alkenes material so that in the Graphene composite polyvinyl alcohol fiber, the content of graphite alkenes material 3wt% with
Under, preferably below 2wt% is more excellent between 0.05wt-1.5wt%.
Preferably, deaeration mode is normal pressure discontinuous degassing or vacuum defoamation, and hot-stretch temperature control is hot at 120-250 DEG C
Draw ratio is 10-37 times, and heat-setting time is 1-15min.
The further double lifting fiber of Graphene composite polyvinyl alcohol fiber prepared using above-mentioned preparation method
Mechanical property, while fiber toughness higher, hot water resistance and antistatic behaviour are assigned, using widely, as strengthening material
Material, construction material have very wide application in the multiple industry such as building trade, carrier.
Compared with prior art, beneficial effects of the present invention are：
(1) preparation method of high performance Graphene composite polyvinyl alcohol fiber, front and rear step linking is tight, and method is simple
Fast, slitless connection can be realized with existing production process equipment and flow, with the excellent of the effective ingredient that can completely retain raw material
Point；
(2) preparation method of the invention is simply easily operated, and operating condition is gentle, is capable of achieving Graphene composite polyvinyl alcohol
The industrialized production of fiber, economic benefit are good, and the fibrous composite prepared is realizing traditional high-strength, high modulus polyvinyl alcohol
On the basis of fiber spinning process, the further mechanical property of double lifting fiber, while imparting higher tough of the fibrous material
Property, hot water resistance and antistatic behaviour；
(3) high performance Graphene composite polyvinyl alcohol tensile strength of fiber of the invention, stretch modulus, elongation at break
Etc. the raising that index has matter, and also fibrous material toughness higher, hot water resistance and antistatic behaviour additionally are imparted, entered
One step expands the market range of application of fibrous material, improves value-added content of product, is conducive to further genralrlization application.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, are
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
The preparation method of high performance Graphene composite polyvinyl alcohol fiber is as follows：
1) graphene oxide, the dispersion liquid that ultrasonic disperse is stablized is added to turn the suspension in 2000rpm in water
First time centrifugation is carried out under speed, centrifugation time 20min removes bottom precipitation, and supernatant is carried out second under 5000rpm rotating speeds
Centrifugation, centrifugation time 10min obtains secondary bottom precipitation, and the secondary bottom precipitation ultrasound that adds water is obtained into the classification oxygen of 1.5wt%
(flake diameter distribution is D90 to graphite alkene sol solutionses：~25 μm)；
2) by concentration for the graphene oxide sol solutionses of 1.5wt% are pre-mixed with the PVA aqueous solution that concentration is 5wt%
(degree of polymerization is 1700, and alcoholysis degree is 99%) to obtain premix, and the premix is mixed again with the PVA aqueous solution of 10wt%
(degree of polymerization is 2500, and alcoholysis degree is 88%), 1h to be stirred at 90 DEG C, adds the 25wt%PVA aqueous solution and BAS, most for conjunction
PVA concentration 15wt%, the aqueous solution of boric acid concentration 2wt% are made into eventually；
3) then introduce ascorbic acid reducing agent 10g, improve temperature to 100 DEG C, continue stir and reductase 12 h, obtain spinning
Stoste (in spinning solution, the concentration of reducing agent is 0.1wt%, and the concentration of PVA is 15wt%), spinning solution is passed through at 90 DEG C
Filtering, after normal pressure discontinuous degassing, is expressed into saltcake coagulating bath through the spinneret orifice of a diameter of 0.1mm, and spun silk becomes just
Raw fiber, pickling, washing, acetalization (glutaraldehyde 1%, 2min, 80 DEG C), drying, heat are carried out to described as-spun fibre
Stretching and thermal finalization treatment, hot-stretch temperature is 140 DEG C, and hot-stretch multiple is 20 times, and heat-setting time is 5min, is finally given
Graphene composite polyvinyl alcohol fiber with superhigh intensity, ultra high modulus performance, graphene oxide content is in fiber
1.5wt%.
Embodiment 2
Be step 1 with the distinctive points of embodiment 1) in sunk from the bottom that obtains is centrifuged under 3000rpm rotating speeds for the first time
Form sediment, adding water, (flake diameter distribution is D90 to the ultrasonic classification graphene oxide sol solutionses for obtaining 2wt%：~30 μm), the spinning for obtaining is former
In liquid, the concentration of reducing agent is 3wt%, and the concentration of PVA is 16wt%, and it is 1.5wt%'s to finally give graphene oxide content
Graphene composite polyvinyl alcohol fiber.
Embodiment 3
Be step 1 with the distinctive points of embodiment 1) in from supernatant is centrifuged under the 7000rpm rotating speeds again after
Secondary supernatant, (flake diameter distribution is D90 to prepare the classification graphene oxide sol solutionses of 3wt%：~5 μm), the spinning for obtaining
In silk stock solution, the concentration of reducing agent is 2wt%, and the concentration of PVA is 15wt%, and finally giving graphene oxide content is
The Graphene composite polyvinyl alcohol fiber of 1.5wt%.
Embodiment 4
Be step 1 with the distinctive points of embodiment 1) in graphene oxide is replaced with into Graphene, secondary bottom precipitation adds
Water ultrasound obtains the classification graphene sol liquid of 1wt%, and (flake diameter distribution is D90：~10 μm), finally give graphene oxide and contain
Measure the Graphene composite polyvinyl alcohol fiber for 1.5wt%.
Embodiment 5
Be step 1 with the distinctive points of embodiment 1) in graphene oxide is replaced with into biomass Graphene, secondary bottom
Precipitation adds water, and (flake diameter distribution is D90 to the ultrasonic classification graphene sol liquid for obtaining 0.5wt%：~12 μm), finally give oxidation
Graphene content is the Graphene composite polyvinyl alcohol fiber of 1.5wt%.
Embodiment 6
Be step 1 with the distinctive points of embodiment 1) in from the supernatant for obtaining is centrifuged for the first time under 2000rpm rotating speeds,
(flake diameter distribution is D90 to obtain the classification graphene oxide sol solutionses of 1.5wt%：~16 μm), finally give graphene oxide and contain
Measure the Graphene composite polyvinyl alcohol fiber of 1.5wt%.
Embodiment 7
Be step 1 with the distinctive points of embodiment 1) in classification graphene oxide sol solutionses concentration be 0.05wt%
(flake diameter distribution is D90：~16 μm)；Step 2) in, by graphene oxide sol solutionses with mass fraction for the PVA of 5wt% is water-soluble
(degree of polymerization is 2000 to liquid, and alcoholysis degree is that 88%) 100 DEG C of PVA for carrying out being pre-mixed stirring 2h, mass fraction is 10wt% are water-soluble
Liquid (degree of polymerization is 2000, alcoholysis degree be 99%) 95 DEG C carry out premixing 2h after obtain premix, by the premix and 25wt%
The PVA aqueous solution and BAS mixed that (degree of polymerization is 2500, and alcoholysis degree is 88%), 1.5h to be stirred at 95 DEG C, finally
It is 20wt%, the aqueous solution of boric acid concentration 5wt%, step 3 to prepare PVA concentration) in reducing agent selection be sodium borohydride, while adding
Plus crosslinking agent glyoxal so that the concentration of reducing agent is 3wt% in spinning solution, and the concentration of crosslinking agent is 0.45wt%, finally
Obtain the Graphene composite polyvinyl alcohol fiber of graphene oxide content 0.05wt%.
Embodiment 8
Be step 1 with the distinctive points of embodiment 1) in classification graphene oxide sol solutionses concentration for 3wt% (piece footpath
It is distributed as D90：~16 μm)；Step 2) in, by graphene oxide sol solutionses with mass fraction for the PVA aqueous solution of 2wt% is (poly-
Right is 2000, alcoholysis degree be 88%) 90 DEG C carry out premixing stirring 1h obtain premix, be by the premix and mass fraction
10wt% the PVA aqueous solution (degree of polymerization is 2000, alcoholysis degree be 99%) 95 DEG C carry out mixing 2h after, then add boric acid and spun
Silk stock solution, in spinning solution, PVA concentration 10wt%, boric acid concentration 4wt%, step 3) in reducing agent selection for hydroiodic acid with it is anti-
Bad hematic acid, while adding crosslinking agent glyoxal and formaldehyde so that the concentration of reducing agent is 2wt% in spinning solution, crosslinking agent
Concentration is 0.0075wt%, finally gives the Graphene composite polyvinyl alcohol fiber of graphene oxide content 3wt%.
Embodiment 9
Be step 1 with the distinctive points of embodiment 1) in from the secondary precipitation for obtaining is centrifuged again under 7000rpm rotating speeds,
(flake diameter distribution is D90 to obtain the classification graphene oxide sol solutionses of 1wt%：~16 μm), finally give graphene oxide content
The Graphene composite polyvinyl alcohol fiber of 1wt%.
Embodiment 10
Be step 1 with the distinctive points of embodiment 1) in from the secondary precipitation for obtaining is centrifuged again under 7000rpm rotating speeds,
(flake diameter distribution is D90 to obtain the classification graphene oxide sol solutionses of 2.5wt%：~16 μm), finally give graphene oxide and contain
Measure the Graphene composite polyvinyl alcohol fiber of 2wt%.
Embodiment 11
It is step 1 with the distinctive points of embodiment 1) it is middle from the precipitation being centrifuged again under 7000rpm rotating speeds, obtain
(flake diameter distribution is D90 to the classification graphene oxide sol solutionses of 2.5wt%：~50 μm), finally give graphene oxide content
The Graphene composite polyvinyl alcohol fiber of 1.5wt%.
Embodiment 12
It is step 1 with the distinctive points of embodiment 1) it is middle from the precipitation being centrifuged again under 7000rpm rotating speeds, obtain
(flake diameter distribution is D90 to the classification graphene oxide sol solutionses of 2.5wt%：~70 μm), finally give graphene oxide content
The Graphene composite polyvinyl alcohol fiber of 1.5wt%.
Comparative example 1
Graphene oxide (the D90 for preparing is added in water：~25 μm), mass fraction is by ultrasonic disperse 1h
The graphene oxide of 1.5wt% be introduced directly into PVA solution (degree of polymerization is 2000, alcoholysis degree be 99%) and BAS in,
PVA concentration is obtained for 15wt%, the aqueous solution of boric acid concentration 2.5wt% stirs 1h at 95 DEG C, introduce 10g ascorbic acid, continues
Stirring 2h, finally gives spinning solution.By spinning solution in filtering is passed through at 90 DEG C, after normal pressure discontinuous degassing, through a diameter of
The spinneret orifice of 0.1mm is expressed into saltcake coagulating bath, and spun silk becomes as-spun fibre, and acid is carried out to described as-spun fibre
Wash, wash, acetalization (glutaraldehyde 1%, 2min, 80 DEG C), drying, hot-stretch and thermal finalization treatment, hot-stretch temperature is
200 DEG C, hot-stretch multiple is 10 times, and heat-setting time is 12min.Finally give the stone that graphene oxide content is 1.5wt%
The fiber of black alkene composite polyvinyl alcohol.
Comparative example 2
Difference with comparative example 1 is that graphene oxide is added in water, the dispersion liquid that ultrasonic disperse is stablized, will
The suspension is centrifuged off bottom precipitation under 1000rpm rotating speeds, and supernatant is centrifuged under 9000rpm rotating speeds and obtains secondary bottom
Precipitation, secondary bottom precipitation is added water, and (flake diameter distribution is D90 to the ultrasonic classification graphene oxide sol solutionses for obtaining 1.5wt%：~
25 μm), the method for follow-up addition PVA solution is consistent with comparative example 1, finally gives the graphite of graphene oxide content 1.5wt%
Alkene composite polyvinyl alcohol fiber.
Comparative example 3
The Graphene composite polyvinyl alcohol prepared using the preparation method of embodiment 1 in patent CN104328533A is fine
Dimension.
Experimental example 1
The property of the Graphene composite polyvinyl alcohol fibrous material that embodiment of the present invention 1-12 and comparative example 1-3 are prepared
Can be contrasted, examination criteria：Tensile strength, Young's modulus and elongation at break use GB/T19975-2005 standards.Tool
Body result is as shown in table 1 below：
The performance parameter of table 1 is contrasted
As can be seen that each side of the Graphene composite polyvinyl alcohol that the embodiment of the present invention is prepared from upper table 1
Can be more excellent, it is suitable to wide popularization and application.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from of the invention
Many other changes and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of preparation method of high performance Graphene composite polyvinyl alcohol fiber, it is characterised in that main to include following step
Suddenly：
(A) the graphite alkenes material aqueous solution is pre-processed, is obtained the graphite alkenes material classification aqueous solution, graphite alkenes material
D90 norm controllings below 70 μm；
(B) the PVA aqueous solution, boric acid and the graphite alkenes material classification aqueous solution are mixed, obtains PVA concentration for 10-
The spinning solution of the boronic acid containing of 20wt%；
(C) after by spinning solution filtering, deaeration, spinning and drying, obtain final product.
2. the preparation method of Graphene composite polyvinyl alcohol fiber according to claim 1, it is characterised in that the step
(A) in, the method for pretreatment includes：Behaviour will be centrifuged under the conditions of graphite alkenes material aqueous solution ultrasonic disperse, 2000-3000rpm
Retain bottom precipitation after work, supernatant respectively obtains secondary bottom precipitation and two after centrifugally operated under the conditions of 5000-7000rpm
Secondary supernatant；
Wherein, the graphite alkenes material classification aqueous solution includes appointing in bottom precipitation, secondary bottom precipitation, secondary supernatant
Meaning one kind is prepared, preferably secondary bottom precipitation；
Preferably, in the graphite alkenes material classification aqueous solution, the concentration of graphite alkenes material is controlled in below 3wt%, more
Preferably below 2wt%.
3. the preparation method of Graphene composite polyvinyl alcohol fiber according to claim 2, it is characterised in that ultrasonic disperse
Time control in 1-3h；
Preferably, under the conditions of 2000-3000rpm the time control of centrifugally operated in 20-40min；
Preferably, under the conditions of 5000-7000rpm the time control of centrifugally operated in 10-30min.
4. the preparation method of the Graphene composite polyvinyl alcohol fiber according to claim any one of 1-3, it is characterised in that
The D90 norm controllings of graphite alkenes material below 50 μm, preferably less than 30 μm, between more preferably 5-25 μm；
Preferably, graphite alkenes material includes Graphene, biomass Graphene, graphene oxide, one kind of Graphene derivative
Or several mixing, the wherein Graphene of Graphene derivative including element doping.
5. the preparation method of Graphene composite polyvinyl alcohol fiber according to claim 1, it is characterised in that the step
(B) in, the PVA aqueous solution several times and gradually steps up the mode of concentration and is added, and initial concentration is controlled between 2-5wt%；
Preferably, after the PVA aqueous solution mixes with the graphite alkenes material classification aqueous solution, then boric acid is added；
Preferably, in the spinning solution, the concentration of PVA is controlled between 15-16wt%；
Preferably, in the spinning solution, the concentration of boric acid is controlled between 2-5wt%.
6. the preparation method of Graphene composite polyvinyl alcohol fiber according to claim 5, it is characterised in that the step
(B) in, in spinning solution, the time control stirred after being added every time when adding the PVA aqueous solution several times is in 1-2h, temperature control
Between 90-100 DEG C.
7. the preparation method of Graphene composite polyvinyl alcohol fiber according to claim 1, it is characterised in that the step
(B) in, the PVA degree of polymerization of the PVA aqueous solution is controlled between 1700-2500, and alcoholysis degree is controlled between 88-99%.
8. the preparation method of Graphene composite polyvinyl alcohol fiber according to claim 1, it is characterised in that the step
(B) in, filtered again after adding crosslinking agent acetalization, reducing agent reduction treatment in spinning solution；
Preferably, crosslinking agent includes one or more mixtures in glyoxal, glutaraldehyde, formaldehyde, boric acid and borax, described
The concentration of crosslinking agent is controlled between 0.0075-0.45wt% in spinning solution；
Preferably, reducing agent includes one or more mixtures in sodium borohydride, ascorbic acid, hydrazine hydrate and hydroiodic acid,
The concentration of reducing agent is controlled between 0.1-3wt% in the spinning solution.
9. the stone for being prepared using the preparation method of the Graphene composite polyvinyl alcohol fiber described in claim any one of 1-8
Black alkene composite polyvinyl alcohol fiber；
Preferably, in the Graphene composite polyvinyl alcohol fiber, the content of graphite alkenes material in below 3wt%, preferably
Below 2wt%, it is more excellent between 0.05wt-1.5wt%.
10. the Graphene composite polyvinyl alcohol fiber described in claim 9 as reinforcing material, construction material building trade,
Application in terms of carrier.
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| CN110085430A (en) * | 2019-04-30 | 2019-08-02 | 宁波石墨烯创新中心有限公司 | A kind of composite coating and its manufacturing method, electrode material |
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| CN115522385B (en) * | 2022-09-28 | 2023-06-09 | 浙江莹隆纤维科技有限公司 | High-strength graphene fiber and preparation method thereof |
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